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CN-115109088-B - Substituted undecene compounds and substituted undecenyl triarylphosphonium halides and methods of making compounds and mixtures thereof

CN115109088BCN 115109088 BCN115109088 BCN 115109088BCN-115109088-B

Abstract

The invention relates to a process for preparing (4Z) -11, 11-dialkoxy-4-undecenyl triarylphosphonium halides of the general formula (3-Z), in which Y represents a halogen atom, ar represents an aryl group, R 1 and R 2 represent, independently of one another, monovalent hydrocarbon radicals having from 1 to 15 carbon atoms, or R 1 and R 2 can together form a divalent hydrocarbon radical R 1 -R 2 having from 2 to 10 carbon atoms, which comprises reacting (7Z) -11-halo-1, 1-dialkoxy-7-undecene compounds of the general formula (1-Z), in which X 1 represents a halogen atom, R 1 and R 2 are as defined above, with phosphine compounds of the general formula (2), in which Ar is as defined above, a phosphonium salt formation reaction taking place to form the compounds (3-Z), and also to compounds L (CH 2 ) 3 CH＝CH(CH 2 ) 5 CH(OR 1 )(OR 2 ) (A) of the general formula (A), in which R 1 and R 2 are as defined above.

Inventors

  • Miyake Hiroyasu
  • JIN SHENGGANG
  • BABA, AKIHIRO

Assignees

  • 信越化学工业株式会社

Dates

Publication Date
20260508
Application Date
20220321
Priority Date
20210323

Claims (16)

  1. 1. A process for preparing a (4Z) -11, 11-dialkoxy-4-undecenyl triarylphosphonium halide of the general formula (3-Z): Wherein Y represents a halogen atom, ar represents an aryl group independently of one another, and R 1 and R 2 represent monovalent hydrocarbon radicals having 1 to 15 carbon atoms, or R 1 and R 2 can together form a divalent hydrocarbon radical R 1 -R 2 having 2 to 10 carbon atoms, The method comprises the following steps: (7Z) -11-halo-1, 1-dialkoxy-7-undecene compounds of the following general formula (1-Z): Wherein X 1 represents a halogen atom, and R 1 and R 2 are as defined above, A phosphonium salt formation reaction with a phosphine compound of the following general formula (2): PAr 3 (2) wherein Ar is as defined above To form (4Z) -11, 11-dialkoxy-4-undecenyl triarylphosphonium halide (3-Z).
  2. 2. A process for preparing a (3 e,5z,9 z) -16, 16-dialkoxy-3, 5, 9-hexadecatriene compound of the following general formula (6): Wherein R 1 and R 2 independently of one another represent monovalent hydrocarbon radicals having from 1 to 15 carbon atoms, or R 1 and R 2 can together form a divalent hydrocarbon radical R 1 -R 2 having from 2 to 10 carbon atoms, The method comprises the following steps: The process for preparing (4Z) -11, 11-dialkoxy-4-undecenyl triarylphosphonium halide (3-Z) according to claim 1, Deprotonating the (4Z) -11, 11-dialkoxy-4-undecenyl triarylphosphonium halide (3-Z) in the presence of a base to form a reaction product mixture, and Subjecting the reaction product mixture to wittig reaction with (2E) -2-pentenal of formula (5): to form (3E, 5Z, 9Z) -16, 16-dialkoxy-3, 5, 9-hexadecatriene compound (6).
  3. 3. A process for preparing (7 z,11z,13 e) -7,11, 13-hexadecatrienal of formula (7): The method comprises the following steps: The process for producing (3 e,5z,9 z) -16, 16-dialkoxy-3, 5, 9-hexadecatriene compound (6) according to claim 2, and Hydrolyzing the (3E, 5Z, 9Z) -16, 16-dialkoxy-3, 5, 9-hexadecatriene compound (6) to form (7Z, 11Z, 13E) -7,11, 13-hexadecatriene aldehyde (7).
  4. 4. A process for preparing a (5 z,9 z) -16, 16-dialkoxy-5, 9-hexadecadiene compound of the following general formula (9): Wherein R 1 and R 2 independently of one another represent monovalent hydrocarbon radicals having from 1 to 15 carbon atoms, or R 1 and R 2 can together form a divalent hydrocarbon radical R 1 -R 2 having from 2 to 10 carbon atoms, The method comprises the following steps: The process for preparing (4Z) -11, 11-dialkoxy-4-undecenyl triarylphosphonium halide (3-Z) according to claim 1, Deprotonating the (4Z) -11, 11-dialkoxy-4-undecenyl triarylphosphonium halide (3-Z) in the presence of a base to form a reaction product mixture, and Allowing the reaction product mixture to undergo wittig with valeraldehyde of formula (8): CH 3 (CH 2 ) 3 CHO (8) To form (5Z, 9Z) -16, 16-dialkoxy-5, 9-hexadecadiene compound (9).
  5. 5. A process for preparing (7 z,11 z) -7, 11-hexadecadienal of formula (10): The method comprises the following steps: The process for producing (5Z, 9Z) -16, 16-dialkoxy-5, 9-hexadecadiene compound (9) according to claim 4, and Hydrolyzing the (5Z, 9Z) -16, 16-dialkoxy-5, 9-hexadecadiene compound (9) to form (7Z, 11Z) -7, 11-hexadecadiene aldehyde (10).
  6. 6. A process for preparing a mixture comprising (3 e,5z,9 z) -16, 16-dialkoxy-3, 5, 9-hexadecatriene compounds of the following general formula (6): Wherein R 1 and R 2 independently of one another represent monovalent hydrocarbon radicals having from 1 to 15 carbon atoms, or R 1 and R 2 can together form a divalent hydrocarbon radical R 1 -R 2 having from 2 to 10 carbon atoms, And (5Z, 9Z) -16, 16-dialkoxy-5, 9-hexadecadiene compound of the following general formula (9): wherein R 1 and R 2 are as defined above, The method comprises the following steps: The process for preparing (4Z) -11, 11-dialkoxy-4-undecenyl triarylphosphonium halide (3-Z) according to claim 1, Deprotonating the (4Z) -11, 11-dialkoxy-4-undecenyl triarylphosphonium halide (3-Z) in the presence of a base to form a reaction product mixture, and Contacting the reaction product mixture with (2E) -2-pentenal of formula (5): And the valeraldehyde of formula (8) below undergoes a wittig reaction: CH 3 (CH 2 ) 3 CHO (8) to form the mixture comprising (3 e,5z,9 z) -16, 16-dialkoxy-3, 5, 9-hexadecatriene compound (6) and (5 z,9 z) -16, 16-dialkoxy-5, 9-hexadecadiene compound (9).
  7. 7. A process for preparing a mixture comprising (7 z,11z,13 e) -7,11, 13-hexadecatrienal of formula (7): And (7Z, 11Z) -7, 11-hexadecadienal of the following formula (10): The method comprises the following steps: The process for producing a mixture comprising (3E, 5Z, 9Z) -16, 16-dialkoxy-3, 5, 9-hexadecatriene compound (6) and (5Z, 9Z) -16, 16-dialkoxy-5, 9-hexadecadiene compound (9), according to claim 6, and Subjecting the mixture comprising the (3 e,5z,9 z) -16, 16-dialkoxy-3, 5, 9-hexadecatriene compound (6) and the (5 z,9 z) -16, 16-dialkoxy-5, 9-hexadecadiene compound (9) to hydrolysis reaction conditions to form a mixture comprising (7 z,11z,13 e) -7,11, 13-hexadecatrienal (7) and (7 z,11 z) -7, 11-hexadecadienal (10).
  8. 8. A process for preparing a (3 e,5z,9 z) -16, 16-dialkoxy-3, 5, 9-hexadecatriene compound of the following general formula (6): Wherein R 1 and R 2 independently of one another represent monovalent hydrocarbon radicals having from 1 to 15 carbon atoms, or R 1 and R 2 can together form a divalent hydrocarbon radical R 1 -R 2 having from 2 to 10 carbon atoms, The method comprises the following steps: Deprotonation of a (4Z) -11, 11-dialkoxy-4-undecenyl triarylphosphonium halide of the general formula (3-Z): wherein Y represents a halogen atom, ar represents an aryl group independently of each other, and R 1 and R 2 are as defined above, To form a reaction product mixture, and Subjecting the reaction product mixture to wittig reaction with (2E) -2-pentenal of formula (5): to form (3E, 5Z, 9Z) -16, 16-dialkoxy-3, 5, 9-hexadecatriene compound (6).
  9. 9. A process for preparing (7 z,11z,13 e) -7,11, 13-hexadecatrienal of the following general formula (7): The method comprises the following steps: The process for producing (3 e,5z,9 z) -16, 16-dialkoxy-3, 5, 9-hexadecatriene compound (6) according to claim 8, and Hydrolyzing the (3E, 5Z, 9Z) -16, 16-dialkoxy-3, 5, 9-hexadecatriene compound (6) to form (7Z, 11Z, 13E) -7,11, 13-hexadecatriene aldehyde (7).
  10. 10. A process for preparing a (5 z,9 z) -16, 16-dialkoxy-5, 9-hexadecadiene compound of the following general formula (9): Wherein R 1 and R 2 independently of one another represent monovalent hydrocarbon radicals having from 1 to 15 carbon atoms, or R 1 and R 2 can together form a divalent hydrocarbon radical R 1 -R 2 having from 2 to 10 carbon atoms, The method comprises the following steps: Deprotonation of a (4Z) -11, 11-dialkoxy-4-undecenyl triarylphosphonium halide of the general formula (3-Z): wherein Y represents a halogen atom, ar represents an aryl group independently of each other, and R 1 and R 2 are as defined above, To form a reaction product mixture, and Allowing the reaction product mixture to undergo wittig with valeraldehyde of formula (8): CH 3 (CH 2 ) 3 CHO (8) To form (5Z, 9Z) -16, 16-dialkoxy-5, 9-hexadecadiene compound (9).
  11. 11. A process for preparing (7 z,11 z) -7, 11-hexadecadienal of formula (10): The method comprises the following steps: The process for producing (5Z, 9Z) -16, 16-dialkoxy-5, 9-hexadecadiene compound (9) according to claim 10, and Hydrolyzing the (5Z, 9Z) -16, 16-dialkoxy-5, 9-hexadecadiene compound (9) to form (7Z, 11Z) -7, 11-hexadecadiene aldehyde (10).
  12. 12. A process for preparing a mixture comprising (3 e,5z,9 z) -16, 16-dialkoxy-3, 5, 9-hexadecatriene compounds of the following general formula (6): Wherein R 1 and R 2 independently of one another represent monovalent hydrocarbon radicals having from 1 to 15 carbon atoms, or R 1 and R 2 can together form a divalent hydrocarbon radical R 1 -R 2 having from 2 to 10 carbon atoms, And (5Z, 9Z) -16, 16-dialkoxy-5, 9-hexadecadiene compound of the following general formula (9): wherein R 1 and R 2 are as defined above, The method comprises the following steps: Deprotonation of a (4Z) -11, 11-dialkoxy-4-undecenyl triarylphosphonium halide of the general formula (3-Z): wherein Y represents a halogen atom, ar represents an aryl group independently of each other, and R 1 and R 2 are as defined above, To form a reaction product mixture, and Contacting the reaction product mixture with (2E) -2-pentenal of formula (5): And the valeraldehyde of formula (8) below undergoes a wittig reaction: CH 3 (CH 2 ) 3 CHO (8) to form a mixture comprising (3E, 5Z, 9Z) -16, 16-dialkoxy-3, 5, 9-hexadecatriene compound (6) and (5Z, 9Z) -16, 16-dialkoxy-5, 9-hexadecadiene compound (9).
  13. 13. A process for preparing a mixture comprising (7 z,11z,13 e) -7,11, 13-hexadecatrienal of formula (7): And (7Z, 11Z) -7, 11-hexadecadienal of the following formula (10): The method comprises the following steps: the process for producing a mixture comprising (3 e,5z,9 z) -16, 16-dialkoxy-3, 5, 9-hexadecatriene compound (6) and (5 z,9 z) -16, 16-dialkoxy-5, 9-hexadecadiene compound (9), according to claim 12, and Subjecting a mixture comprising the (3 e,5z,9 z) -16, 16-dialkoxy-3, 5, 9-hexadecatriene compound (6) and the (5 z,9 z) -16, 16-dialkoxy-5, 9-hexadecadiene compound (9) to hydrolysis reaction conditions to form a mixture comprising (7 z,11z,13 e) -7,11, 13-hexadecatrienal (7) and (7 z,11 z) -7, 11-hexadecadienal (10).
  14. 14. A compound of the general formula (a): L(CH 2 ) 3 CH＝CH(CH 2 ) 5 CH(OR 1 )(OR 2 ) (A) Wherein R 1 and R 2 independently of each other represent a monovalent hydrocarbon group having 1 to 15 carbon atoms, or R 1 and R 2 may together form a divalent hydrocarbon group R 1 -R 2 having 2 to 10 carbon atoms, L represents X 1 or Y - Ar 3 P + , wherein X 1 and Y represent halogen atoms, and Ar independently of each other represent an aryl group.
  15. 15. The compound of claim 14, wherein the compound is a 11-halo-1, 1-dialkoxy-7-undecene compound of the following general formula (1): X 1 (CH 2 ) 3 CH＝CH(CH 2 ) 5 CH(OR 1 )(OR 2 ) (1)。
  16. 16. The compound of claim 14, wherein the compound is an 11, 11-dialkoxy-4-undecenyl triarylphosphonium halide of the following general formula (3): Y - Ar 3 P + (CH 2 ) 3 CH＝CH(CH 2 ) 5 CH(OR 1 )(OR 2 ) (3).

Description

Substituted undecene compounds and substituted undecenyl triarylphosphonium halides and methods of making compounds and mixtures thereof Technical Field The present invention relates to 11-halo-1, 1-dialkoxy-7-undecene compounds and methods of preparing 11, 11-dialkoxy-4-undecenyl triarylphosphonium halides, trialkenylaldehyde compounds, and dienal compounds therefrom. The invention also relates to 11, 11-dialkoxy-4-undecenyl triarylphosphonium halides and to methods for producing trialkenal compounds and dienal compounds therefrom. Background Citrus leaf miners (Phyllocnistis citrella) are one of the most serious pests of citrus, in north america, middle america and south america such as the united states, brazil and argentina, in mediterranean countries such as spanish and italy, asia such as japan, taiwan, indonesia, philippines and india, oceangoin such as australia, middle eastern countries such as sauter, and africa such as synopsis and south africa. The leaf miner infects and damages the leaf, seriously affects the growth of small trees and saplings. Holes dug by pests can lead to the development of citrus canker. Therefore, prevention and control of citrus leaf miner is very important. In addition, the leaf miner intrudes into mesophyll, and thus, the pesticide applied by a typical spray method cannot reach the pests, and thus it is difficult to control the pests with the pesticide. Because of the concern about pesticide residues, biological control methods are attracting attention, and the use of sex pheromone substances is expected to become one of them. The sex pheromone component of citrus leaf miner is reported to be an aldehyde having 16 carbon atoms, specifically a 3:1 mixture of (7 z,11z,13 e) -7,11, 13-hexadecatrienal and (7 z,11 z) -7, 11-hexadecadienal in a region other than japan (non-patent documents 1 and 2 listed below), and is only (7 z,11 z) -7, 11-hexadecadienal in japan (non-patent document 3 listed below). A method for producing (7Z, 11Z, 13E) -7,11, 13-hexadecatrienal is described in non-patent document 1 listed below. In this process, the starting material 2- (5-bromopentyl) -1, 3-dioxane was iodinated with sodium iodide in acetone to form 2- (5-iodopentyl) -1, 3-dioxane. Next, the 2- (5-iodopentyl) -1, 3-dioxane thus obtained was subjected to a coupling reaction with (5-chloro-1-pentyn-1-yl) lithium in hexamethylphosphoric triamide (HMPA) and Tetrahydrofuran (THF) to form 2- (10-chloro-6-dec-1-yl) -1, 3-dioxane. Next, the 2- (10-chloro-6-dec-1-yl) -1, 3-dioxane thus obtained was reacted with potassium acetate in HMPA to form 10- (1, 3-dioxan-2-yl) -4-decynyl acetate. Subsequently, the 10- (1, 3-dioxan-2-yl) -4-decynyl acetate thus obtained was subjected to a hydrogenation reaction using 5% of palladium-barium sulfate as a catalyst and quinoline as a catalyst poison to reduce the carbon-carbon triple bond to a carbon-carbon double bond, thereby forming (4Z) -10- (1, 3-dioxan-2-yl) -4-decynyl acetate. Next, the (4Z) -10- (1, 3-dioxan-2-yl) -4-decenyl acetate thus obtained was hydrolyzed with an aqueous potassium hydroxide solution in methanol to form (4Z) -10- (1, 3-dioxan-2-yl) -4-decen-1-ol. The hydroxy group of (4Z) -10- (1, 3-dioxan-2-yl) -4-decen-1-ol thus obtained is oxidized with Pyridine Dichromate (PDC) in methylene chloride to form (4Z) -10- (1, 3-dioxan-2-yl) -4-decenal. The (4Z) -10- (1, 3-dioxan-2-yl) -4-decenal thus obtained undergoes a Wittig reaction with independently prepared triphenylphosphine (2E) -2-pentenylide in THF and HMPA to form 2- (6Z, 10Z, 12E) -6,10,12-pentadec-trien-1-yl-1, 3-dioxan. Subsequently, the 2- (6Z, 10Z, 12E) -6,10,12-pentadecatrien-1-yl-1, 3-dioxane thus obtained was reacted with methanol in the presence of p-toluenesulfonic acid to form (3E, 5Z, 9Z) -16, 16-dimethoxy-3, 5, 9-hexadecatrien. Finally, the (3E, 5Z, 9Z) -16, 16-dimethoxy-3, 5, 9-hexadecatriene thus obtained is hydrolyzed with hydrochloric acid in THF. Another method for producing (7Z, 11Z, 13E) -7,11, 13-hexadecatrienal is described in non-patent document 2 listed below. In this process, the hydroxyl group of the starting material 3-bromo-1-propanol is protected to form 1-bromo-3- (tert-butyldimethylsilyloxy) propane. Next, separately prepared tetrahydro-2- (7-octyn-1-yloxy) -2H-pyran is reacted with N-butyllithium in THF, then with 1-bromo-3- (tert-butyldimethylsilyloxy) propane obtained above in a mixture of THF and N, N' -Dimethylpropylurea (DMPU) to form 1- (tert-butyldimethylsilyloxy) -11- (tetrahydropyranyloxy) -4-undecyne. The tert-butyldimethylsilyl group of 1- (tert-butyldimethylsilyloxy) -11- (tetrahydropyranyloxy) -4-undecyne thus obtained was removed in THF using tetra-n-butylammonium fluoride (TBAF), and the resulting compound was subjected to hydrogenation reaction using nickel boride (P-2 Ni) as a catalyst to reduce the carbon-carbon triple bond to a carbon-carbon double bond, thereby forming (4Z) -11- (tetrahydropyranyloxy) -4-undecen-1-ol. The hydroxy group